Carbon Dioxide - Wikipedia, The Free Encyclopedia

17/10/2014 Carbon dioxide - Wikipedia, the free encyclopedia
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Carbon dioxide
Carbonic acid gas
Carbonic anhydride
Carbonic oxide
Carbon oxide
Carbon(IV) oxide
Dry ice (solid phase)
Identifiers
CAS number
124-38-9

PubChem 280
ChemSpider
274

UNII
142M471B3J

EC number 204-696-9
UN number 1013
KEGG
D00004

MeSH Carbon+dioxide
ChEBI
CHEBI:16526

ChEMBL
CHEMBL1231871

RTECS number FF6400000
ATC code V03AN02
(http://www.whocc.no/atc_ddd_index/?
code=V03AN02)
Beilstein
Reference
1900390
Gmelin
Reference
989
3DMet B01131
Jmol-3D images Image 1
(http://chemapps.stolaf.edu/jmol/jmol.php?
model=O%3DC%3DO)
Carbon dioxide
From Wikipedia, the free encyclopedia
Carbon dioxide (chemical formula CO
2
) is a
naturally occurring chemical compound
composed of 2 oxygen atoms each covalently
double bonded to a single carbon atom. It is a
gas at standard temperature and pressure and
exists in Earth's atmosphere in this state, as a
trace gas at a concentration of 0.04 per cent (400
ppm) by volume, as of 2014.
[1]
As part of the carbon cycle, plants, algae, and
cyanobacteria use light energy to
photosynthesize carbohydrate from carbon
dioxide and water, with oxygen produced as a
waste product.
[2]
However, photosynthesis
cannot occur in darkness and at night some
carbon dioxide is produced by plants during
respiration.
[3]
It is produced during the
respiration of all other aerobic organisms and is
exhaled in the breath of air-breathing land
animals, including humans. Carbon dioxide is
produced during the processes of decay of
organic materials and the fermentation of sugars
in beer and winemaking. It is produced by
combustion of wood, carbohydrates and major
carbon- and hydrocarbon-rich fossil fuels such
as coal, peat, petroleum and natural gas. It is
emitted from volcanoes, hot springs and geysers
and is freed from carbonate rocks by dissolution
in water and acids. CO
2
is found in lakes, at
depth under the sea and commingled with oil
and gas deposits.
[4]
The environmental effects of carbon dioxide are
of significant interest. Atmospheric carbon
dioxide is the primary source of carbon in life on
Earth and its concentration in Earth's pre-
industrial atmosphere since late in the
Precambrian eon was regulated by
photosynthetic organisms. Carbon dioxide is an
important greenhouse gas and burning of
carbon-based fuels since the industrial
revolution has rapidly increased its
concentration in the atmosphere, leading to
global warming. It is also a major source of
ocean acidification since it dissolves in water to
form carbonic acid.
[5]
Other names
Image 2
(http://chemapps.stolaf.edu/jmol/jmol.php?
model=C%28%3DO%29%3DO)
Properties
Molecular
formula
CO
2
Molar mass 44.01 g mol1
Appearance Colorless gas
Odor Odorless
Density 1562 kg/m3
(solid at 1 atm and 78.5 C)
770 kg/m3
(liquid at 56 atm and 20 C)
1.977 kg/m3
(gas at 1 atm and 0 C)
Melting point 56.6 C; 69.8 F; 216.6 K (Triple point
at 5.1 atm)
Sublimation
conditions
78.5 C; 109.2 F; 194.7 K (1 atm)
Solubility in
water
1.45 g/L at 25 C, 100 kPa
Vapor pressure 5.73 MPa (20 C)
Acidity (pK
a
) 6.35, 10.33
Refractive index
(n
D
)
1.1120
Viscosity 0.07 cP at 78.5 C
Dipole moment 0 D
Structure
Crystal structure trigonal
Molecular shape linear
Thermochemistry
Specific
heat capacity C
37.135 J/K mol
Std molar
entropy

S
o
298
214 Jmol1K1
Std enthalpy of
formation
f
H
o
298
393.5 kJmol1
Hazards
MSDS External MSDS
NFPA 704
Contents
1 History
2 Chemical and physical properties
2.1 Structure and bonding
2.2 In aqueous solution
2.3 Chemical reactions of CO
2
2.4 Physical properties
3 Isolation and production
3.1 Laboratory methods
3.2 Industrial production
4 Uses
4.1 Precursor to chemicals
4.2 Foods
4.2.1 Beverages
4.2.2 Wine making
4.3 Inert gas
4.4 Fire extinguisher
4.5 Supercritical CO
2
as solvent
4.6 Agricultural and biological
applications
4.7 Oil recovery
4.8 Bio transformation into fuel
4.9 Refrigerant
4.10 Coal bed methane recovery
4.11 Niche uses
5 In the Earth's atmosphere
6 In the oceans
7 Biological role
7.1 Photosynthesis and carbon
fixation
7.2 Toxicity
7.3 Human physiology
7.3.1 Content
7.3.2 Transport in the blood
7.3.3 Regulation of
respiration
SMILES
InChI
Related compounds
Other anions Carbon disulfide
Carbon diselenide
Other cations Silicon dioxide
Germanium dioxide
Tin dioxide
Lead dioxide
Related carbon
oxides
Carbon monoxide
Carbon suboxide
Dicarbon monoxide
Carbon trioxide
Related
compounds
Carbonic acid
Carbonyl sulfide
Supplementary data page
Structure and
properties
n,
r
, etc.
Thermodynamic
data
Phase behaviour
Solid, liquid, gas
Spectral data UV, IR, NMR, MS
Except where noted otherwise, data are given for materials
in their standard state (at 25 C (77 F), 100 kPa)
(verify) (what is: / ?)
Infobox references
Crystal structure of dry ice
8 See also
9 References
10 Further reading
11 External links
History
Carbon dioxide
was one of the
first gases to be
described as a
substance
distinct from air.
In the
seventeenth
century, the
Flemish chemist
Jan Baptist van
Helmont
observed that when he burned charcoal in a
closed vessel, the mass of the resulting ash was
much less than that of the original charcoal. His
interpretation was that the rest of the charcoal
had been transmuted into an invisible substance
he termed a "gas" or "wild spirit" (spiritus
sylvestre).
[6]
The properties of carbon dioxide were studied
more thoroughly in the 1750s by the Scottish physician Joseph Black. He found that limestone (calcium
carbonate) could be heated or treated with acids to yield a gas he called "fixed air." He observed that the
fixed air was denser than air and supported neither flame nor animal life. Black also found that when
bubbled through limewater (a saturated aqueous solution of calcium hydroxide), it would precipitate
calcium carbonate. He used this phenomenon to illustrate that carbon dioxide is produced by animal
respiration and microbial fermentation. In 1772, English chemist Joseph Priestley published a paper
entitled Impregnating Water with Fixed Air in which he described a process of dripping sulfuric acid (or
oil of vitriol as Priestley knew it) on chalk in order to produce carbon dioxide, and forcing the gas to
dissolve by agitating a bowl of water in contact with the gas.
[7]
Carbon dioxide was first liquefied (at elevated pressures) in 1823 by Humphry Davy and Michael
Faraday.
[8]
The earliest description of solid carbon dioxide was given by Adrien-Jean-Pierre Thilorier,
who in 1835 opened a pressurized container of liquid carbon dioxide, only to find that the cooling
produced by the rapid evaporation of the liquid yielded a "snow" of solid CO
2
.
[9]
Chemical and physical properties
Structure and bonding
0
1 0
The carbon dioxide molecule is linear and centrosymmetric. The two C=O bonds are equivalent and are
short (116.3 pm), consistent with double bonding.
[10]
Since it is centrosymmetric, the molecule has no
electrical dipole. Consistent with this fact, only two vibrational bands are observed in the IR spectrum
an antisymmetric stretching mode at 2349 cm
1
and a bending mode near 666 cm
1
. There is also a
symmetric stretching mode at 1388 cm
1
which is only observed in the Raman spectrum.
In aqueous solution
Carbon dioxide is soluble in water, in which it reversibly forms H
2
CO
3
(carbonic acid), which is a weak
acid since its ionization in water is incomplete.
CO
2
+ H
2
O H
2
CO
3
The hydration equilibrium constant of carbonic acid is (at
25 C). Hence, the majority of the carbon dioxide is not converted into carbonic acid, but remains as
CO
2
molecules, not affecting the pH.
The relative concentrations of CO
2
, H
2
CO
3
, and the deprotonated forms HCO
3
(bicarbonate) and
CO
2
3
(carbonate) depend on the pH. As shown in a Bjerrum plot, in neutral or slightly alkaline water
(pH > 6.5), the bicarbonate form predominates (>50%) becoming the most prevalent (>95%) at the pH
of seawater. In very alkaline water (pH > 10.4), the predominant (>50%) form is carbonate. The oceans,
being mildly alkaline with typical pH = 8.28.5, contain about 120 mg of bicarbonate per liter.
Being diprotic, carbonic acid has two acid dissociation constants, the first one for the dissociation into
the bicarbonate (also called hydrogen carbonate) ion (HCO
3
):
H
2
CO
3
HCO
3
+ H
+
K
a1
= 2.5 10
4
mol/litre; pK
a1
= 3.6 at 25 C.
[10]
This is the true first acid dissociation constant, defined as , where the
denominator includes only covalently bound H
2
CO
3
and excludes hydrated CO
2
(aq). The much smaller
and often-quoted value near 4.16 10
7
is an apparent value calculated on the (incorrect) assumption
that all dissolved CO
2
is present as carbonic acid, so that
. Since most of the dissolved CO
2
remains as CO
2
molecules, K
a1
(apparent) has a much larger denominator and a much smaller value than the true K
a1
.
[11]
Carbon dioxide pressure-temperature
phase diagram showing the triple
point and critical point of carbon
dioxide
Sample of solid carbon dioxide or
"dry ice" pellets
The bicarbonate ion is an amphoteric species that can act as an acid or as a base, depending on pH of the
solution. At high pH, it dissociates significantly into the carbonate ion (CO
3
2
):
HCO
3
CO
3
2
+ H
+
K
a2
= 4.69 10
11
mol/litre; pK
a2
= 10.329
In organisms carbonic acid production is catalysed by the enzyme, carbonic anhydrase.
Chemical reactions of CO
2
CO
2
is a weak electrophile. Its reaction with basic water illustrates this property, in which case
hydroxide is the nucleophile. Other nucleophiles react as well. For example, carbanions as provided by
Grignard reagents and organolithium compounds react with CO
2
to give carboxylates:
MR + CO
2
RCO
2
M
where M = Li or MgBr and R = alkyl or aryl.
In metal carbon dioxide complexes, CO
2
serves as a ligand, which can facilitate the conversion of CO
2
to other chemicals.
[12]
The reduction of CO
2
to CO is ordinarily a difficult and slow reaction:
CO
2
+ 2 e
+ 2H
+
CO + H
2
O
The redox potential for this reaction near pH 7 is about 0.53 V versus the standard hydrogen electrode.
The nickel-containing enzyme carbon monoxide dehydrogenase catalyses this process.
[13]
Physical properties
Carbon dioxide is
colorless. At low
concentrations, the gas is
odorless. At higher
concentrations it has a
sharp, acidic odor. At
standard temperature and
pressure, the density of
carbon dioxide is around
1.98 kg/m
3
, about 1.67
times that of air.
Carbon dioxide has no
liquid state at pressures
below 5.1 standard atmospheres (520 kPa). At 1 atmosphere
(near mean sea level pressure), the gas deposits directly to a solid
at temperatures below 78.5 C (109.3 F; 194.7 K) and the solid sublimes directly to a gas above
78.5 C. In its solid state, carbon dioxide is commonly called dry ice.
Liquid carbon dioxide forms only at pressures above 5.1 atm; the triple point of carbon dioxide is about
518 kPa at 56.6 C (see phase diagram, above). The critical point is 7.38 MPa at 31.1 C.
[14]
Another
form of solid carbon dioxide observed at high pressure is an amorphous glass-like solid.
[15]
This form of
glass, called carbonia, is produced by supercooling heated CO
2
at extreme pressure (4048 GPa or about
400,000 atmospheres) in a diamond anvil. This discovery confirmed the theory that carbon dioxide could
exist in a glass state similar to other members of its elemental family, like silicon (silica glass) and
germanium dioxide. Unlike silica and germania glasses, however, carbonia glass is not stable at normal
pressures and reverts to gas when pressure is released.
At temperatures and pressures above the critical point, carbon dioxide behaves as a supercritical fluid
known as supercritical carbon dioxide.
Isolation and production
Carbon dioxide is mainly produced as an unrecovered side product of four technologies: combustion of
fossil fuels, production of hydrogen by steam reforming, ammonia synthesis, and fermentation. It can be
obtained by distillation from air, but this method is inefficient.
The combustion of all carbon-containing fuels, such as methane (natural gas), petroleum distillates
(gasoline, diesel, kerosene, propane), coal, wood and generic organic matter produces carbon dioxide
and, in most cases, water. As an example the chemical reaction between methane and oxygen is given
below.
CH
4
+ 2 O
2
CO
2
+ 2 H
2
O
Quicklime (CaO), a compound that has many industrial uses, is produced by driving off CO
2
from
limestone by heating (calcining) at about 850 C:
CaCO
3
CaO + CO
2
Iron is reduced from its oxides with coke in a blast furnace, producing pig iron and carbon dioxide:
[16]
Fe
2
O
3
+ 3 CO 2 Fe + 3 CO
2
Yeast metabolizes sugar to produce carbon dioxide and ethanol, also known as alcohol, in the production
of wines, beers and other spirits, but also in the production of bioethanol:
C
6
H
12
O
6
2 CO
2
+ 2 C
2
H
5
OH
All aerobic organisms produce CO
2
when they oxidize carbohydrates, fatty acids, and proteins in the
mitochondria of cells. The large number of reactions involved are exceedingly complex and not
described easily. Refer to (cellular respiration, anaerobic respiration and photosynthesis). The equation
for the respiration of glucose and other monosaccharides is:
C
6
H
12
O
6
+ 6 O
2
6 CO
2
+ 6 H
2
O
Carbon dioxide bubbles in a soft drink.
Photoautotrophs (i.e. plants and cyanobacteria) use the energy contained in sunlight to photosynthesize
simple sugars from CO
2
absorbed from the air and water:
n CO
2
+ n H
2
O (CH
2
O) + n O
2
Laboratory methods
A variety of chemical routes to carbon dioxide are known, such as the reaction between most acids and
most metal carbonates. For example, the reaction between hydrochloric acid and calcium carbonate
(limestone or chalk) is depicted below:
CaCO + 2 HCl CaCl
2
+ H
2
CO
3
The carbonic acid (H
2
CO
3
) then decomposes to water and CO
2
:
H
2
CO
3
CO
2
+ H
2
O
Such reactions are accompanied by foaming or bubbling, or both. In industry such reactions are
widespread because they can be used to neutralize waste acid streams.
Industrial production
Industrial carbon dioxide can be produced by several methods, many of which are practiced at various
scales.
[17]
In its dominant route, carbon dioxide is produced as a side product of the industrial production
of ammonia and hydrogen. These processes begin with the reaction of water and natural gas (mainly
methane).
[18]
Although carbon dioxide is not often recovered, carbon dioxide results from combustion of fossil fuels
and wood as well fermentation of sugar in the brewing of beer, whisky and other alcoholic beverages. It
also results from thermal decomposition of limestone, CaCO
3
, in the manufacture of lime (calcium
oxide, CaO). It may be obtained directly from natural carbon dioxide springs, where it is produced by
the action of acidified water on limestone or dolomite.
Uses
Carbon dioxide is used by the food industry, the oil industry,
and the chemical industry.
[17]
Precursor to chemicals
In the chemical industry, carbon dioxide is mainly consumed
as an ingredient in the production of urea and methanol.
Metal carbonates and bicarbonates, as well as some
carboxylic acids derivatives (e.g., sodium salicylate) are
prepared using CO
2
.
Foods
Carbon dioxide is a food additive used as a propellant and acidity regulator in the food industry. It is
approved for usage in the EU
[19]
(listed as E number E290), USA
[20]
and Australia and New Zealand
[21]
(listed by its INS number 290).
A candy called Pop Rocks is pressurized with carbon dioxide gas at about 4 x 10
6
Pa (40 bar, 580 psi).
When placed in the mouth, it dissolves (just like other hard candy) and releases the gas bubbles with an
audible pop.
Leavening agents cause dough to rise by producing carbon dioxide. Baker's yeast produces carbon
dioxide by fermentation of sugars within the dough, while chemical leaveners such as baking powder
and baking soda release carbon dioxide when heated or if exposed to acids.
Beverages
Carbon dioxide is used to produce carbonated soft drinks and soda water. Traditionally, the carbonation
in beer and sparkling wine came about through natural fermentation, but many manufacturers carbonate
these drinks with carbon dioxide recovered from the fermentation process. In the case of bottled and
kegged beer, the most common method used is carbonation with recycled carbon dioxide. With the
exception of British Real Ale, draught beer is usually transferred from kegs in a cold room or cellar to
dispensing taps on the bar using pressurized carbon dioxide, sometimes mixed with nitrogen.
Wine making
Carbon dioxide in the form of dry ice is often used in the wine making process to cool down bunches of
grapes quickly after picking to help prevent spontaneous fermentation by wild yeast. The main
advantage of using dry ice over regular water ice is that it cools the grapes without adding any additional
water that may decrease the sugar concentration in the grape must, and therefore also decrease the
alcohol concentration in the finished wine.
Dry ice is also used during the cold soak phase of the wine making process to keep grapes cool. The
carbon dioxide gas that results from the sublimation of the dry ice tends to settle to the bottom of tanks
because it is denser than air. The settled carbon dioxide gas creates a hypoxic environment which helps
to prevent bacteria from growing on the grapes until it is time to start the fermentation with the desired
strain of yeast.
Carbon dioxide is also used to create a hypoxic environment for carbonic maceration, the process used
to produce Beaujolais wine.
Carbon dioxide is sometimes used to top up wine bottles or other storage vessels such as barrels to
prevent oxidation, though it has the problem that it can dissolve into the wine, making a previously still
wine slightly fizzy. For this reason, other gases such as nitrogen or argon are preferred for this process
by professional wine makers.
Inert gas
It is one of the most commonly used compressed gases for pneumatic (pressurized gas) systems in
portable pressure tools. Carbon dioxide is also used as an atmosphere for welding, although in the
welding arc, it reacts to oxidize most metals. Use in the automotive industry is common despite
significant evidence that welds made in carbon dioxide are more brittle than those made in more inert
atmospheres, and that such weld joints deteriorate over time because of the formation of carbonic acid. It
is used as a welding gas primarily because it is much less expensive than more inert gases such as argon
or helium. When used for MIG welding, CO
2
use is sometimes referred to as MAG welding, for Metal
Active Gas, as CO
2
can react at these high temperatures. It tends to produce a hotter puddle than truly
inert atmospheres, improving the flow characteristics. Although, this may be due to atmospheric
reactions occurring at the puddle site. This is usually the opposite of the desired effect when welding, as
it tends to embrittle the site, but may not be a problem for general mild steel welding, where ultimate
ductility is not a major concern.
It is used in many consumer products that require pressurized gas because it is inexpensive and
nonflammable, and because it undergoes a phase transition from gas to liquid at room temperature at an
attainable pressure of approximately 60 bar (870 psi, 59 atm), allowing far more carbon dioxide to fit in
a given container than otherwise would. Life jackets often contain canisters of pressured carbon dioxide
for quick inflation. Aluminium capsules of CO
2
are also sold as supplies of compressed gas for airguns,
paintball markers, inflating bicycle tires, and for making carbonated water. Rapid vaporization of liquid
carbon dioxide is used for blasting in coal mines. High concentrations of carbon dioxide can also be used
to kill pests. Liquid carbon dioxide is used in supercritical drying of some food products and
technological materials, in the preparation of specimens for scanning electron microscopy and in the
decaffeination of coffee beans.
Fire extinguisher
Carbon dioxide extinguishes flames, and some fire extinguishers, especially those designed for electrical
fires, contain liquid carbon dioxide under pressure. Carbon dioxide extinguishers work well on small
flammable liquid and electrical fires, but not on ordinary combustible fires, because although it excludes
oxygen, it does not cool the burning substances significantly and when the carbon dioxide disperses they
are free to catch fire upon exposure to atmospheric oxygen. Carbon dioxide has also been widely used as
an extinguishing agent in fixed fire protection systems for local application of specific hazards and total
flooding of a protected space.
[22]
International Maritime Organization standards also recognize carbon
dioxide systems for fire protection of ship holds and engine rooms. Carbon dioxide based fire protection
systems have been linked to several deaths, because it can cause suffocation in sufficiently high
concentrations. A review of CO
2
systems identified 51 incidents between 1975 and the date of the
report, causing 72 deaths and 145 injuries.
[23]
Supercritical CO
2
as solvent
Liquid carbon dioxide is a good solvent for many lipophilic organic compounds and is used to remove
caffeine from coffee. Carbon dioxide has attracted attention in the pharmaceutical and other chemical
processing industries as a less toxic alternative to more traditional solvents such as organochlorides. It is
used by some dry cleaners for this reason (see green chemistry).
Agricultural and biological applications
Plants require carbon dioxide to conduct photosynthesis. Greenhouses may (if of large size, must) enrich
their atmospheres with additional CO
2
to sustain and increase plant growth.
[24][25]
A photosynthesis-
related drop (by a factor less than two) in carbon dioxide concentration in a greenhouse compartment
would kill green plants, or, at least, completely stop their growth. At very high concentrations (100 times
atmospheric concentration, or greater), carbon dioxide can be toxic to animal life, so raising the
Comparison of phase diagrams of carbon dioxide (red) and water
(blue) as a log-lin chart with phase transitions points at 1 atmosphere
concentration to 10,000 ppm (1%) or higher for several hours will eliminate pests such as whiteflies and
spider mites in a greenhouse.
[26]
Carbon dioxide is used in greenhouses as the main carbon source for
Spirulina algae.
In medicine, up to 5% carbon dioxide (130 times atmospheric concentration) is added to oxygen for
stimulation of breathing after apnea and to stabilize the O
2
/CO
2
balance in blood.
It has been proposed that carbon dioxide from power generation be bubbled into ponds to grow algae
that could then be converted into biodiesel fuel.
[27]
Oil recovery
Carbon dioxide is used in enhanced oil recovery where it is injected into or adjacent to producing oil
wells, usually under supercritical conditions, when it becomes miscible with the oil. This approach can
increase original oil recovery by reducing residual oil saturation by between 7 per cent to 23 per cent
additional to primary extraction.
[28]
It acts as both a pressurizing agent and, when dissolved into the
underground crude oil, significantly reduces its viscosity, and changing surface chemistry enabling the
oil to flow more rapidly through the reservoir to the removal well.
[29]
In mature oil fields, extensive pipe
networks are used to carry the carbon dioxide to the injection points.
Bio transformation into fuel
Researchers have genetically modified a strain of the cyanobacterium Synechococcus elongatus to
produce the fuels isobutyraldehyde and isobutanol from CO
2
using photosynthesis.
[30]
Refrigerant
Liquid and solid carbon dioxide are
important refrigerants, especially in
the food industry, where they are
employed during the transportation
and storage of ice cream and other
frozen foods. Solid carbon dioxide is
called "dry ice" and is used for small
shipments where refrigeration
equipment is not practical. Solid
carbon dioxide is always below
78.5 C at regular atmospheric
pressure, regardless of the air
temperature.
Liquid carbon dioxide (industry nomenclature R744 or R-744) was used as a refrigerant prior to the
discovery of R-12 and may enjoy a renaissance due to the fact that R134a contributes to climate change.
Its physical properties are highly favorable for cooling, refrigeration, and heating purposes, having a
high volumetric cooling capacity. Due to its operation at pressures of up to 130 bar (1880 psi), CO
2
systems require highly resistant components that have already been developed for mass production in
many sectors. In automobile air conditioning, in more than 90% of all driving conditions for latitudes
higher than 50, R744 operates more efficiently than systems using R134a. Its environmental advantages
(GWP of 1, non-ozone depleting, non-toxic, non-flammable) could make it the future working fluid to
A carbon dioxide laser.
replace current HFCs in cars, supermarkets, hot water heat pumps, among others. Coca-Cola has fielded
CO
2
-based beverage coolers and the U.S. Army is interested in CO
2
refrigeration and heating
technology.
[31][32]
The global automobile industry is expected to decide on the next-generation refrigerant in car air
conditioning. CO
2
is one discussed option.(see Sustainable automotive air conditioning)
Coal bed methane recovery
In enhanced coal bed methane recovery, carbon dioxide would be pumped into the coal seam to displace
methane, as opposed to current methods which primarily rely on the removal of water (to reduce
pressure) to make the coal seam release its trapped methane.
[33]
Niche uses
Carbon dioxide is so inexpensive and so innocuous,
that it finds many small uses that represent what
might be called niche uses. For example it is used in
the carbon dioxide laser, which is one of the earliest
type of lasers.
Carbon dioxide can be used as a means of
controlling the pH of swimming pools, by
continuously adding gas to the water, thus keeping
the pH level from rising. Among the advantages of
this is the avoidance of handling (more hazardous)
acids. Similarly, it is also used in the maintaining
reef aquaria, where it is commonly used in calcium reactors to temporarily lower the pH of water being
passed over calcium carbonate in order to allow the calcium carbonate to dissolve into the water more
freely where it is used by some corals to build their skeleton. It is also used as the primary coolant in
advanced gas-cooled reactors in the nuclear power generation industry.
Carbon dioxide induction is commonly used for the euthanasia of laboratory research animals. Methods
to administer CO
2
include placing animals directly into a closed, prefilled chamber containing CO
2
, or
exposure to a gradually increasing concentration of CO
2
. In 2013, the American Veterinary Medical
Association issued new guidelines for carbon dioxide induction, stating that a flow rate of 10% to 30%
volume/min is optimal for the humane euthanization of small rodents.
[34]
In the Earth's atmosphere
Carbon dioxide in Earth's atmosphere is considered a trace gas currently occurring at an average
concentration of about 400 parts per million by volume
[1]
(or 591 parts per million by mass). The total
mass of atmospheric carbon dioxide is 3.1610
15
kg (about 3,000 gigatonnes). Its concentration varies
seasonally (see graph at right) and also considerably on a regional basis, especially near the ground. In
urban areas concentrations are generally higher and indoors they can reach 10 times background levels.
Carbon dioxide is a greenhouse gas.
The Keeling Curve of atmospheric CO
2
concentrations measured at Mauna Loa
Observatory.
Yearly increase of atmospheric CO
2
:
In the 1960s, the average annual
increase was 37% of the 20002007
average.
[35]
As of March 2014, carbon dioxide in the Earth's atmosphere is at a concentration of approximately 400
ppm by volume.
[1]
Atmospheric concentrations of carbon dioxide fluctuate slightly with the change of
the seasons, driven primarily by seasonal plant growth in the Northern Hemisphere. Concentrations of
carbon dioxide fall during the northern spring and summer as plants consume the gas, and rise during the
northern autumn and winter as plants go dormant, die and decay. Taking all this into account, the
concentration of CO
2
grew by about 2 ppm in 2009.
[36]
"The main cause of the current global warming
trend is human expansion of the "greenhouse effect" warming that results when the atmosphere traps
heat radiating from Earth toward space."
[37]
Carbon dioxide is a greenhouse gas as it is transparent to
incoming visible
light from the
sun, but absorbs
outgoing
infrared
radiation from
the ground at its
two infrared-
active
vibrational
frequencies (see
Structure and
bonding above).
As for all gases,
the absorbed
energy can be
redistributed by molecular collisions which heat the
atmosphere.
[38]
Before the advent of release of carbon dioxide to the atmosphere by humans, concentrations tended to
increase with increasing global temperatures, acting as a positive feedback for changes induced by other
processes such as orbital cycles.
[39]
There is a seasonal cycle in CO
2
concentration associated primarily
with the Northern Hemisphere growing season.
[40]
Five hundred million years ago carbon dioxide was 20 times more prevalent than today, decreasing to 4
5 times during the Jurassic period and then slowly declining with a particularly swift reduction occurring
49 million years ago.
[41][42]
Human activities such as the combustion of fossil fuels and deforestation
have caused the atmospheric concentration of carbon dioxide to increase by about 35% since the
beginning of the age of industrialization.
[43]
Up to 40% of the gas emitted by some volcanoes during subaerial eruptions is carbon dioxide.
[44]
It is
estimated that volcanoes release about 130230 million tonnes (145255 million short tons) of CO
2
into
the atmosphere each year. Carbon dioxide is also produced by hot springs such as those at the Bossoleto
site near Rapolano Terme in Tuscany, Italy. Here, in a bowl-shaped depression of about 100 m diameter,
local concentrations of CO
2
rise to above 75% overnight, sufficient to kill insects and small animals, but
it warms rapidly when sunlit and the gas is dispersed by convection during the day.
[45]
Locally high
concentrations of CO
2
, produced by disturbance of deep lake water saturated with CO
2
are thought to
have caused 37 fatalities at Lake Monoun, Cameroon in 1984 and 1700 casualties at Lake Nyos,
Cameroon in 1986.
[46]
Emissions of CO
2
by human activities are estimated to be 135 times greater than
the quantity emitted by volcanoes.
[47]
The cement industry is one of the three primary producers of carbon dioxide along with the energy
production and transportation industries. As of 2011 concrete contributes 7% to global anthropogenic
CO
2
emissions.
[48]
In the oceans
Carbon dioxide dissolves in the ocean to form carbonic acid (H
2
CO
3
), bicarbonate (HCO
3
) and
carbonate (CO
3
2
), and there is about fifty times as much carbon dissolved in the sea water of the oceans
as exists in the atmosphere. The oceans act as an enormous carbon sink, and have taken up about a third
of CO
2
emitted by human activity.
[49]
As the concentration of carbon dioxide increases in the atmosphere, the increased uptake of carbon
dioxide into the oceans is causing a measurable decrease in the pH of the oceans which is referred to as
ocean acidification. Although the natural absorption of CO
2
by the world's oceans helps mitigate the
climatic effects of anthropogenic emissions of CO
2
, it also results in a decrease in the pH of the oceans.
This reduction in pH impacts the biological systems in the oceans, primarily oceanic calcifying
organisms. These impacts span the food chain from autotrophs to heterotrophs and include organisms
such as coccolithophores, corals, foraminifera, echinoderms, crustaceans and molluscs. Under normal
conditions, calcite and aragonite are stable in surface waters since the carbonate ion is at supersaturating
concentrations. However, as ocean pH falls, so does the concentration of this ion, and when carbonate
becomes undersaturated, structures made of calcium carbonate are vulnerable to dissolution. Even if
there is no change in the rate of calcification, therefore, the rate of dissolution of calcareous material
increases.
[50]
Corals,
[51][52][53]
coccolithophore algae,
[54][55][56][57]
coralline algae,
[58]
foraminifera,
[59]
shellfish
[60]
and
pteropods
[61]
experience reduced calcification or enhanced dissolution when exposed to elevated CO
2
.
Gas solubility decreases as the temperature of water increases (except when both pressure exceeds 300
bar and temperature exceeds 393 K, only found near deep geothermal vents)
[62]
and therefore the rate of
uptake from the atmosphere decreases as ocean temperatures rise.
Most of the CO
2
taken up by the ocean, which is about 30% of the total released into the atmosphere,
[63]
forms carbonic acid in equilibrium with bicarbonate. Some of these chemical species are consumed by
photosynthetic organisms, that remove carbon from the cycle. Increased CO
2
in the atmosphere has led
to decreasing alkalinity of seawater, and there is concern that this may adversely affect organisms living
in the water. In particular, with decreasing alkalinity, the availability of carbonates for forming shells
decreases,
[64]
although there's evidence of increased shell production by certain species under increased
CO
2
content.
[65]
NOAA states in their May 2008 "State of the science fact sheet for ocean acidification" that:
"The oceans have absorbed about 50% of the carbon dioxide (CO
2
) released from the burning of fossil
fuels, resulting in chemical reactions that lower ocean pH. This has caused an increase in hydrogen ion
(acidity) of about 30% since the start of the industrial age through a process known as "ocean
acidification." A growing number of studies have demonstrated adverse impacts on marine organisms,
including:
The rate at which reef-building corals produce their skeletons decreases, while production of
numerous varieties of jellyfish increases.
The ability of marine algae and free-swimming zooplankton to maintain protective shells is
reduced.
The survival of larval marine species, including commercial fish and shellfish, is reduced."
Also, the Intergovernmental Panel on Climate Change (IPCC) writes in their Climate Change 2007:
Synthesis Report:
[66]
"The uptake of anthropogenic carbon since 1750 has led to the ocean becoming more acidic with an
average decrease in pH of 0.1 units. Increasing atmospheric CO
2
concentrations lead to further
acidification ... While the effects of observed ocean acidification on the marine biosphere are as yet
undocumented, the progressive acidification of oceans is expected to have negative impacts on marine
shell-forming organisms (e.g. corals) and their dependent species."
Some marine calcifying organisms (including coral reefs) have been singled out by major research
agencies, including NOAA, OSPAR commission, NANOOS and the IPCC, because their most current
research shows that ocean acidification should be expected to impact them negatively.
[67]
Carbon dioxide is also introduced into the oceans through hydrothermal vents. The Champagne
hydrothermal vent, found at the Northwest Eifuku volcano at Marianas Trench Marine National
Monument, produces almost pure liquid carbon dioxide, one of only two known sites in the world.
[68]
Sea urchins have been discovered to be able to convert carbon dioxide into raw material for their
shells.
[69]
Biological role
Carbon dioxide is an end product of cellular respiration in organisms that obtain energy by breaking
down sugars, fats and amino acids with oxygen as part of their metabolism. This includes all plants,
algae and animals and aerobic fungi and bacteria. In vertebrates, the carbon dioxide travels in the blood
from the body's tissues to the skin (e.g., amphibians) or the gills (e.g., fish), from where it dissolves in
the water, or to the lungs from where it is exhaled. During active photosynthesis, plants can absorb more
carbon dioxide from the atmosphere than they use in respiration.
Photosynthesis and carbon fixation
Carbon fixation is a biochemical process by which atmospheric carbon dioxide is incorporated by plants,
algae and (cyanobacteria) into energy-rich organic molecules such as glucose, thus creating their own
food by photosynthesis. Photosynthesis uses carbon dioxide and water to produce sugars from which
other organic compounds can be constructed, and oxygen is produced as a by-product.
Overview of photosynthesis and
respiration. Carbon dioxide (at
right), together with water, form
oxygen and organic compounds
(at left) by photosynthesis, which
can be respired to water and
(CO
2
).
Figure 2. Overview of the Calvin cycle and carbon
fixation
Ribulose-1,5-bisphosphate carboxylase oxygenase, commonly abbreviated to RuBisCO, is the enzyme
involved in the first major step of carbon fixation, the production of two molecules of 3-
phosphoglycerate from CO
2
and ribulose bisphosphate, as shown in the diagram at left.
RuBisCo is thought to be the single most abundant protein on Earth.
[70]
Phototrophs use
the products of
their
photosynthesis
as internal food
sources and as
raw material for
the biosynthesis
of more
complex organic
molecules, such
as
polysaccharides,
nucleic acids
and proteins.
These are used
for their own
growth, and also
as the basis of the food chains and webs that feed other organisms,
including animals such as ourselves. Some important phototrophs,
the coccolithophores synthesise hard calcium carbonate scales. A
globally significant species of coccolithophore is Emiliania huxleyi whose calcite scales have formed the
basis of many sedimentary rocks such as limestone, where what was previously atmospheric carbon can
remain fixed for geological timescales.
Plants can grow up to 50 percent faster in concentrations of 1,000 ppm CO
2
when compared with
ambient conditions, though this assumes no change in climate and no limitation on other nutrients.
[71]
Elevated CO
2
levels cause increased growth reflected in the harvestable yield of crops, with wheat, rice
and soybean all showing increases in yield of 1214% under elevated CO
2
in FACE experiments.
[72][73]
Increased atmospheric CO
2
concentrations result in fewer stomata developing on plants
[74]
which leads
to reduced water usage and increased water-use efficiency.
[75]
Studies using FACE have shown that CO
2
enrichment leads to decreased concentrations of micronutrients in crop plants.
[76]
This may have knock-
on effects on other parts of ecosystems as herbivores will need to eat more food to gain the same amount
of protein.
[77]
The concentration of secondary metabolites such as phenylpropanoids and flavonoids can also be altered
in plants exposed to high concentrations of CO
2
.
[78][79]
Main symptoms of carbon dioxide toxicity, by
increasing volume percent in air.
[83]
Plants also emit CO
2
during respiration, and so the majority of plants and algae, which use C3
photosynthesis, are only net absorbers during the day. Though a growing forest will absorb many tons of
CO
2
each year, a mature forest will produce as much CO
2
from respiration and decomposition of dead
specimens (e.g., fallen branches) as is used in photosynthesis in growing plants.
[80]
Contrary to the long-
standing view that they are carbon neutral, mature forests can continue to accumulate carbon
[81]
and
remain valuable carbon sinks, helping to maintain the carbon balance of the Earth's atmosphere.
Additionally, and crucially to life on earth, photosynthesis by phytoplankton consumes dissolved CO
2
in
the upper ocean and thereby promotes the absorption of CO
2
from the atmosphere.
[82]
Toxicity
Carbon dioxide content in fresh air (averaged between
sea-level and 10 kPa level, i.e., about 30 km altitude)
varies between 0.036% (360 ppm) and 0.039% (390
ppm), depending on the location.
[84]
CO
2
is an asphyxiant gas and not classified as toxic or
harmful in accordance with Globally Harmonized System
of Classification and Labelling of Chemicals standards of
United Nations Economic Commission for Europe by
using the OECD Guidelines for the Testing of Chemicals.
In concentrations up to 1% (10,000 ppm), it will make
some people feel drowsy.
[83]
Concentrations of 7% to
10% may cause suffocation, even in the presence of
sufficient oxygen, manifesting as dizziness, headache,
visual and hearing dysfunction, and unconsciousness
within a few minutes to an hour.
[85]
The physiological
effects of acute carbon dioxide exposure are grouped together under the term hypercapnia, a subset of
asphyxiation.
Because it is heavier than air, in locations where the gas seeps from the ground (due to sub-surface
volcanic or geothermal activity) in relatively high concentrations, without the dispersing effects of wind,
it can collect in sheltered/pocketed locations below average ground level, causing animals located
therein to be suffocated. Carrion feeders attracted to the carcasses are then also killed. Children have
been killed in the same way near the city of Goma by CO
2
emissions from the nearby volcano Mt.
Nyiragongo.
[86]
The Swahili term for this phenomenon is 'mazuku'.
Adaptation to increased concentrations of CO
2
occurs in humans. Continuous inhalation of CO
2
can be
tolerated at three percent inspired concentrations for at least one month and four percent inspired
concentrations for over a week. It was suggested that 2.0 percent inspired concentrations could be used
for closed air spaces (e.g. a submarine) since the adaptation is physiological and reversible. Decrement
in performance or in normal physical activity does not happen at this level.
[87][88]
However, submarines
have carbon dioxide scrubbers which reduce a significant amount of the CO
2
present.
[89]
Miners, who are particularly vulnerable to gas exposure, referred to mixtures of carbon dioxide and
nitrogen as "blackdamp," "choke damp" or "stythe." Before more effective technologies were developed,
miners would frequently monitor for dangerous levels of blackdamp and other gases in mine shafts by
bringing a caged canary with them as they worked. The canary is more sensitive to asphyxiant gases
than humans, and as it became unconscious would stop singing and fall off its perch. The Davy lamp
could also detect high levels of blackdamp (which sinks, and collects near the floor) by burning less
brightly, while methane, another suffocating gas and explosion risk, would make the lamp burn more
brightly.
Carbon dioxide differential above outdoor concentrations at steady state conditions (when the occupancy
and ventilation system operation are sufficiently long that CO
2
concentration has stabilized) are
sometimes used to estimate ventilation rates per person. CO
2
is considered to be a surrogate for human
bio-effluents and may correlate with other indoor pollutants. Higher CO
2
concentrations are associated
with occupant health, comfort and performance degradation. ASHRAE Standard 62.12007 ventilation
rates may result in indoor levels up to 2,100 ppm above ambient outdoor conditions. Thus if the outdoor
ambient is 400 ppm, indoor concentrations may reach 2,500 ppm with ventilation rates that meet this
industry consensus standard. Concentrations in poorly ventilated spaces can be found even higher than
this (range of 3,000 or 4,000).
Human physiology
Content
The body produces approximately 2.3 pounds (1.0 kg) of carbon dioxide per day per person,
[90]
containing 0.63 pounds (290 g) of carbon.
In humans, this carbon dioxide is carried through the venous system and is breathed out through the
lungs. Therefore, the carbon dioxide content in the body is high in the venous system, and decreases in
the respiratory system, resulting in lower concentrations along any arterial system. Carbon dioxide
content of the blood is often given as the partial pressure, which is the pressure which carbon dioxide
would have had if it alone occupied the volume.
[91]
In humans, the carbon dioxide contents are as follows:
Reference ranges or averages for partial pressures of carbon dioxide
(abbreviated PCO
2
)
Unit Venous blood gas
Alveolar pulmonary
gas pressures
Arterial blood carbon dioxide
kPa
5.5
[92]
-6.8
[92]
4.8
4.7
[92]
-6.0
[92]
mmHg 4151 36
35
[93]
-45
[93]
Transport in the blood
CO
2
is carried in blood in three different ways. (The exact percentages vary depending whether it is
arterial or venous blood).
Most of it (about 70% to 80%) is converted to bicarbonate ions HCO
3
by the enzyme carbonic
anhydrase in the red blood cells,
[94]
by the reaction CO
2
+ H
2
O H
2
CO
3
H
+
+ HCO
3
.
5% 10% is dissolved in the plasma
[94]
5% 10% is bound to hemoglobin as carbamino compounds
[94]
Hemoglobin, the main oxygen-carrying molecule in red blood cells, carries both oxygen and carbon
dioxide. However, the CO
2
bound to hemoglobin does not bind to the same site as oxygen. Instead, it
combines with the N-terminal groups on the four globin chains. However, because of allosteric effects
on the hemoglobin molecule, the binding of CO
2
decreases the amount of oxygen that is bound for a
given partial pressure of oxygen. The decreased binding to carbon dioxide in the blood due to increased
oxygen levels is known as the Haldane Effect, and is important in the transport of carbon dioxide from
the tissues to the lungs. Conversely, a rise in the partial pressure of CO
2
or a lower pH will cause
offloading of oxygen from hemoglobin, which is known as the Bohr Effect.
Regulation of respiration
Carbon dioxide is one of the mediators of local autoregulation of blood supply. If its levels are high, the
capillaries expand to allow a greater blood flow to that tissue.
Bicarbonate ions are crucial for regulating blood pH. A person's breathing rate influences the level of
CO
2
in their blood. Breathing that is too slow or shallow causes respiratory acidosis, while breathing that
is too rapid leads to hyperventilation, which can cause respiratory alkalosis.
Although the body requires oxygen for metabolism, low oxygen levels normally do not stimulate
breathing. Rather, breathing is stimulated by higher carbon dioxide levels. As a result, breathing low-
pressure air or a gas mixture with no oxygen at all (such as pure nitrogen) can lead to loss of
consciousness without ever experiencing air hunger. This is especially perilous for high-altitude fighter
pilots. It is also why flight attendants instruct passengers, in case of loss of cabin pressure, to apply the
oxygen mask to themselves first before helping others; otherwise, one risks losing consciousness.
[94]
The respiratory centers try to maintain an arterial CO
2
pressure of 40 mm Hg. With intentional
hyperventilation, the CO
2
content of arterial blood may be lowered to 1020 mm Hg (the oxygen content
of the blood is little affected), and the respiratory drive is diminished. This is why one can hold one's
breath longer after hyperventilating than without hyperventilating. This carries the risk that
unconsciousness may result before the need to breathe becomes overwhelming, which is why
hyperventilation is particularly dangerous before free diving.
See also
Carbon monoxide
Bosch reaction
Bottled gas
Carbogen
Carbon dioxide sensor
CO
2
sequestration
EcoCute As refrigerants
Emission standards
Industrial gas
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Kaya identity
Lake Kivu
List of least carbon efficient power stations
List of countries by carbon dioxide emissions
Meromictic lake
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a

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c

d
Derived from mmHg values using 0.133322 kPa/mmHg
Further reading
Shendell, Prill, Fisk, Apte1, Blake & Faulkner, Associations between classroom CO
2
concentrations and student attendance in Washington and Idaho, Indoor Air 2004.
Seppanen, Fisk and Mendell, Association of Ventilation Rates and CO
2
Concentrations with
Health and Other Responses in Commercial and Institutional Buildings, Indoor Air 1999.
External links
International Chemical Safety Card 0021
(http://www.inchem.org/documents/icsc/icsc/eics0021.htm)
CID 280 (http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=280) from PubChem
Carbon dioxide MSDS (http://sdsdata.org/68399) by Amerigas in the SDSdata.org database.
CDC NIOSH Pocket Guide to Chemical Hazards Carbon Dioxide
(http://www.cdc.gov/niosh/npg/npgd0103.html)
CO
2
Carbon Dioxide Properties, Uses, Applications (http://www.uigi.com/carbondioxide.html)
Dry Ice information (http://www.dryiceinfo.com/science.htm)
Trends in Atmospheric Carbon Dioxide (http://www.cmdl.noaa.gov/ccgg/trends/) (NOAA)
"A War Gas That Saves Lives." (http://books.google.com/books?
id=RicDAAAAMBAJ&pg=PA53) Popular Science, June 1942, pp. 5357.
NASA's Orbiting Carbon Observatory (http://oco.jpl.nasa.gov/)
The on-line catalogue of CO
2
natural emissions in Italy (http://googas.ov.ingv.it/)
Reactions, Thermochemistry, Uses, and Function of Carbon Dioxide (http://www.chemistry-
reference.com/q_compounds.asp?CAS=124-38-9)
Carbon Dioxide Part One (http://www.periodicvideos.com/videos/mv_carbon_dioxide_one.htm)
and Carbon Dioxide Part Two
(http://www.periodicvideos.com/videos/mv_carbon_dioxide_two.htm) at The Periodic Table of
Videos (University of Nottingham)
Retrieved from "http://en.wikipedia.org/w/index.php?title=Carbon_dioxide&oldid=629715568"
Categories: Acid anhydrides Acidic oxides Carbon dioxide Coolants Fire suppression agents
Greenhouse gases Household chemicals Inorganic solvents Laser gain media
93. ^
a

b
Normal Reference Range Table
(http://web.archive.org/web/20111225185659/http://pathcuric1.swmed.edu/pathdemo/nrrt.htm). University of
Texas Southwestern Medical Center at Dallas. Used in Interactive Case Study Companion to Pathologic basis
of disease.
94. ^
a

b

c

d
"Carbon dioxide" (http://www.solarnavigator.net/solar_cola/carbon_dioxide.htm). solarnavigator.net.
Retrieved 2007-10-12.
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